The invention relates to new compounds of the class 3,3,5,5-tetramethyl-2-oxo-1,4-piperazine, polymers thereof, the use of the novel compounds or polymers as stabilizers for organic material against harmful effects of light, oxygen and/or heat, and organic material stabilized correspondingly.
Structure and numbering of 3,3,5,5-tetramethyl-2-oxo-1,4-piperazine is as shown in the formula: 
It has now been found, that certain compounds containing one or more moieties of the type 3,3,5,5-tetramethyl-2-oxo-1,4-piperazine-1-yl bonded via an oxygen atom are especially well suitable as stabilizers for organic materials.
The invention therefore relates to a compound of the formula (I) 
wherein
p is zero or 1;
q and r, independently of each other, are an integer from 1 to 6; and
s is a number ranging from 1 to 8;
X is xe2x80x94Oxe2x80x94 or, when p is 1, X is also a group 
Rw, Rx, Ry and Rz are, independently of each other, C1-C18alkyl, C5-C12cycloalkyl or C1-C5hydroxyalkyl, especially methyl;
R1 is hydrogen; C1-C18alkyl; oxyl; OH; CH2CN; C1-C18alkoxy; C5-C12cycloalkoxy; C3-C8alkenyl; C3-C8alkynyl; C7-C12phenylalkyl; C7-C15phenylalkyl, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C1-C4alkyl and C1-C4alkoxy; C7-C15phenylalkoxy; C7-C15phenylalkoxy, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C1-C4alkyl and C1-C4alkoxy; or R1 is C1-C8alkanoyl; C3-C5alkenoyl; C1C18alkanoyloxy; glycidyl; or a group xe2x80x94CH2CH(OH)xe2x80x94G, in which G is hydrogen, methyl or phenyl;
R2 and R6, independently of each other, are hydrogen, C1-C8alkyl, C5-C12cycloalkyl or C1-C4hydroxyalkyl;
R3, R4, R5, R7, R8, R9, independently of each other, are hydrogen, C1-C8alkyl or C5-C12cycloalkyl;
when s is 1,
W is C1-C18alkyl; C2-C18alkyl which is substituted by NH2, NHR10, N(R10)2, nitro, hydroxy and/or ORxe2x80x213; or W is C5-C12cycloalkyl; C5-C12cycloalkyl which is substituted by OH, C1-C4alkyl or C1-C4alkoxy; C3-C6alkenyl; C3-C12epoxyalkyl; C7-C15phenylalkyl which is unsubstituted or substituted on the phenyl ring by a radical selected from C1-C4alkyl and C1-C4alkoxy; or W is one of the groups of the formulae (IIa)-(IIe) 
or, when R1 is a group xe2x80x94CH2CH(OH)xe2x80x94G, W may also be hydrogen;
R10 is hydrogen, C1-C8alkyl, C5-C12cycloalkyl, C7-C15phenylalkyl which is unsubstituted or substituted on the phenyl ring by a radical selected from C1-C4alkyl and C1-C4alkoxy;
R11 is hydrogen; C1-C17alkyl; C1-C12alkyl substituted by OH, C1-C12alkoxy and/or a residue benzophenonyl or benzophenonyloxy, wherein one or both phenyl rings of the benzophenone moiety are unsubstituted or substituted by OH, halogen, C1-C4alkyl and/or C1-C18alkoxy; or R11 is C5-C12cycloalkyl which is unsubstituted or substituted by C1-C4alkyl; C2-C17alkenyl; phenyl; phenyl substituted by NH2, NHR10, N(R10)2, or C1-C4alkyl or C1-C4alkoxy; C7-C15phenylalkyl; C8-C15phenylalkenyl; or C7-C15phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or C1-C4alkoxy;
R12 is a direct bond or C1-C12alkylene; phenylene; cyclohexylene;
R13 is C1-C18alkyl; C2-C18alkyl which is substituted by NH2, NHR10, N(R10)2, nitro, hydroxy and/or OR13; C3-C18alkenyl; C5-C12cycloalkyl; C5-C12cycloalkyl which is substituted by C1-C4alkyl and/or interrupted by xe2x80x94Oxe2x80x94; and when W is a group (IId) and when W is a group (IIb) while R12 is not a direct bond, R13 can be also hydrogen, or one equivalent of a cation of groups Ia or IIa of the periodic system, especially sodium or potassium;
Rxe2x80x213 is C1-C18alkyl; C2-C18alkyl which is substituted by NH2, NHR10, N(R10)2, nitro, hydroxy and/or OR13; C3-C18alkenyl; C5-C12cycloalkyl; C5-C12cycloalkyl which is substituted by C1-C4alkyl and/or interrupted by xe2x80x94Oxe2x80x94;
R14 is C1-C18alkyl; C2-C18alkyl which is substituted by NH2, NHR10, N(R10)2, hydroxy and/or OR13; C5-C12cycloalkyl which is unsubstituted or substituted by C1-C4alkyl and/or interrupted by xe2x80x94Oxe2x80x94; or C7-C15phenylalkyl which is unsubstituted or substituted on the phenyl ring by a radical selected from C1-C4alkyl and C1-C4alkoxy;
R15 is a direct bond; C1-C20alkylene; C2-C10alkenylene; C2-C8alkenylene substituted by C6-C12aryl or C6-C12aryl which is substituted by C1-C8alkyl, C1-C8alkoxy, di(C1-C4-alkyl)amino, nitro, thienyl, phenoxyphenyl, phenylthiophenyl, benzo[b]thiophen-2-yl, benzofuran-2-yl, 9H-fluorenyl, biphenylyl, 10H-phenothiazinyl; C2-C4oxaalkylene; C5-C7cycloalkylene; C5-C7cycloalkenylene or phenylene;
when s is 2
W is C2-C12alkylene; C4-C12alkylene substituted by OH and/or interrupted by oxygen or sulfur or xe2x80x94NR10xe2x80x94; C4-C12alkenylene; C6-C12alkenylene substituted by OH and/or interrupted by O; C5-C7cycloalkylene; C5-C7cycloalkylene-di(C1-C4alkylene); C1-C4alkylene-di(C5-C7cycloalkylene); phenylene di(C1-C4alkylene); or one of the groups of the formulae (IIIa)-(IIIh)
xe2x80x94COxe2x80x94R18xe2x80x94COxe2x80x83xe2x80x83(IIIa);
xe2x80x94COOxe2x80x94R19xe2x80x94OOCxe2x80x94xe2x80x83xe2x80x83(IIIb);
xe2x80x94CONHxe2x80x94R20xe2x80x94NHCOxe2x80x94xe2x80x83xe2x80x83(IIIc);

in which Hal stands for halogen or C1-C4alkoxy;
R18 is a direct bond; C1-C12alkylene; C2-C12alkylene interrupted by oxygen, sulfur and/or xe2x80x94NR10xe2x80x94; C5-C7cycloalkylene; C5-C7cycloalkenylene; or phenylene; C2-C8alkenylene; C2-C8alkenylene substituted by C4-C12aryl or C4-C12aryl which is substituted by C1-C8alkyl, C1-C8alkoxy, di(C1-C4-alkyl)amino, nitro; or C2-C8alkenylene substituted by thienyl, phenoxyphenyl, phenylthiophenyl, benzo[b]thiophen-2-yl, benzofuran-2-yl, 9H-fluorenyl, biphenylyl, 10H-phenothiazinyl, thiofuranyl;
R19 is C2-C12alkylene; C4-C12alkylene interrupted by 1, 2 or 3 oxygen atoms; C5-C7cycloalkylene; C5-C7cycloalkylene di(C1-C4alkylene); or C1-C4alkylidene di(C5-C7cycloalkylene);
R20 is C2-C12alkylene; C5-C7cycloalkylene; phenylene;
Rxe2x80x220 is C2-C12alkylene; C5-C7cycloalkylene; phenylene; and if i is 1, Rxe2x80x220 additionally embraces methylene;
i is zero or 1;
t is zero or an integer from 1 to 7;
v and z, independently of each other, are an integer from 1 to 4;
when s is 3
W is aliphatic C4-C18triacyl; cycloaliphatic C6-C18triacyl or aromatic C9-C18triacyl; 1,3,5triazine-2,4,6-triyl; or a group of the formulae (IVa-IVb) 
where R22, R23, R24, independently of each other, are C1-C7alkylene;
when s is 4
W is aliphatic C5-C18tetraacyl; cycloaliphatic C8-C18tetraacyl or aromatic C10-C18tetraacyl or a tetravalent residue of the formula Va
Z1xe2x80x94NR10xe2x80x94R20xe2x80x94NR10xe2x80x94Z2,xe2x80x83xe2x80x83(Va)
wherein Z1 and Z2 are each, independently of one another, a group of the formula Vb, Vc or Vd 
and the group of formula Vb-d is attached via a bond from the triazine ring to the nitrogen atom in formula Va;
when s is 5, W is aliphatic C7-C18pentaacyl; cycloaliphatic C10-C18pentaacyl or aromatic C11-C18pentaacyl;
when s is 6, W is aliphatic C8-C18hexaacyl; cycloaliphatic or aromatic C12-C18hexaacyl or a hexavalent residue of the formula VIa
Z1xe2x80x94NR10xe2x80x94R20xe2x80x94N(Z2)xe2x80x94R20xe2x80x94NR10xe2x80x94Z3xe2x80x83xe2x80x83(VIa)
wherein Z1, Z2 and Z3, independently of one another, are a group of the formula Vb, Vc or Vd, which is attached via a bond from the triazine ring to the nitrogen atom in formula VIa;
when s is 7, W is aliphatic, cycloaliphatic or aromatic C12-C18heptaacyl;
when s is 8, W is aliphatic, cycloaliphatic or aromatic C12-C18octaacyl or a residue of the formula VIIa
Z1xe2x80x94NR10xe2x80x94R20xe2x80x94N(Z2)xe2x80x94R20xe2x80x94N(Z3)xe2x80x94R20xe2x80x94NR10xe2x80x94Z4xe2x80x83xe2x80x83(VIIa)
wherein Z1, Z2, Z3 and Z4, independently of one another, are a group of the formula Vb, Vc or Vd, which is attached via a bond from the triazine ring to the nitrogen atom in formula VIIa; and
Xxe2x80x2 is xe2x80x94Oxe2x80x94 or xe2x80x94N(R10)xe2x80x94.
Where one compound carries more than one group denoted with the same symbol, these groups may be the same or different within their defined meanings.
W as an aliphatic, cycloaliphatic or aromatic acyl group of valency s stands for a residue Rxe2x80x94(COxe2x80x94)s, where R embraces, for example, within the definition given as an aliphatic residue alkyl or alkenyl, or alkyl or alkenyl substituted by OH or COOR13 or interrupted by O; as a cycloaliphatic residue C5-C12cycloalkyl, especially cyclohexyl, or a corresponding 5 or 6 membered oxa-cycloalkyl moiety, or said C5-C12cycloalkyl or oxa-cycloalkyl moiety substituted by C1-C4alkyl, OH, C1-C4hydroxyalkyl or COOR13; as an aromatic residue phenyl, naphthyl or biphenyl, or phenylalkyl, phenylalkenyl, naphthylalkyl, naphthylalkenyl, biphenylalkyl, biphenylalkenyl; or said aromatic residues substituted by COOR13.
Of special importance among these acyl residues Rxe2x80x94(COxe2x80x94)s are when s is 1, W as a group of the above formula (IIb) or (IId) or a group of the formula (IIxe2x80x2a) or (IIxe2x80x2c): 
when s is 2, an acyl residue of formula IIIa with R as R18, especially C1-C12alkylene; C4-C12alkylene; C4-C12alkylene interrupted by oxygen, sulfur and/or xe2x80x94NR10xe2x80x94; C5-C7cycloalkylene; phenylene; C2-C8alkenylene; C2-C8alkenylene substituted by phenyl or a residue thiophene, e.g. 
when s is 4, R as phenyl, C4-C6alkyl or C4-C6alkenyl or a group of the formulae (Vc-Vd) 
when s is 6, R as a 1,2,3,4,5,6-cyclohexane hexacarboxy, or a residue of the formula 
Preferably, s is 1, 2, 3, 4, 6 or 8; more preferably 1-4 or 6; most preferably 2-4 or 6.
Alkylene, cycloalkylene or alkenylene residues may be bonded on different carbon atoms or on the same carbon atom thus embracing alkylidene, cycloalkylidene and alkenylidene, respectively.
R15 as C2-C10alkenylene is preferably a group 
or a group 
where R16 is C3-C8alkenyl; and R17 is hydrogen or C1-C8alkyl.
Halogen atoms are preferably chloro or bromo, especially chloro.
R1 is preferably hydrogen; C1-C8alkyl, especially methyl; oxyl; OH; C1-C18alkoxy, especially C3-C12alkoxy; C5-C12cycloalkoxy, especially cyclohexyloxy; C3-C8alkenyl; C3-C8alkynyl, e.g. propargyl; C7-C12phenylalkyl, e.g. benzyl; C7-C15phenylalkoxy; C1-C8alkanoyl, especially acetyl; C3-C5alkenoyl, especially (meth)acryloyl; glycidyl; or a group xe2x80x94CH2CH(OH)xe2x80x94G, in which G is hydrogen, methyl or phenyl.
Aryl stands for an organic residue obeying the Hueckel rule, i.e. containing 4n+2 xcfx80-electrons per molecular unit, where n is an integer. Thus, C4-C12aryl usually is heteroaryl, where heteroatoms are mostly N, O or S, or hydrocarbon C6-C12aryl. C4aryl groups are, for example, furanyl, thiophenyl, pyrrolyl; C6-C12aryl is, for example, phenyl or naphthyl. Especially preferred is thiophenyl or phenyl.
Groups which may be unsubstituted or substituted by selected radicals such as C6-C12aryl or C5-C12cycloalkyl, like a phenyl or a cyclohexyl ring, are preferably unsubstituted or mono-, di- or tri-substituted, especially preferred are these groups unsubstituted or mono- or disubstituted.
A preferred residue C3-C12epoxyalkyl is glycidyl.
Open bonds in alkylene or cycloalkylene residues may be attached on different carbon atoms or on the same carbon atom, thus embracing alkylidene or cycloalkylidene. Alkylidene and cycloalkylidene are saturated divalent hydrocarbons having both open bonds localized on the same carbon atom; for instance, C1-C4alkylidene embraces C1alkylidene which is methylene.
Alkyl is a monovalent residue of the formula CnH(2n+1) wherein n denotes the number of carbon atoms. Alkylene, alkanetriyl, alkanetetrayl, alkanepentayl, alkanehexayl, alkaneheptayl, alkaneoctayl are corresponding di, tri, tetra, penta, hexa, hepta or octovalent alkanes wherein each bond reduces the number of hydrogen atoms in the general formula CnH(2n+2) by 1.
Alkanoyl is a branched or unbranched radical, typically, within the definitions given, formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, eicosanoyl or docosanoyl. Alkanoyl of 2 to 18, in particular of 2 to 12, e.g. of 2 to 6, carbon atoms is preferred. Acetyl is particularly preferred.
Alkanoyloxy is oxygen-capped alkanoyl; preferences are mainly as can be derived from alkanoyl above.
Alkenoyl is a branched or unbranched radical, typically embracing, within the definitions given, propenoyl, 2-butenoyl, 3-butenoyl, isobutenoyl, n-2,4-pentadienoyl, 3-methyl-2-butenoyl, n-2-octenoyl, n-2-dodecenoyl, isododecenoyl, oleoyl, n-2-octadecenoyl or n-4-octadecenoyl. Alkenoyl of 3 to 18, preferably of 3 to 12, e.g. of 3 to 6, most preferably of 3 to 4, carbon atoms is preferred.
Alkenoyloxy is oxygen-capped alkenoyl; preferences are mainly as can be derived from alkenoyl above.
Alkyl is a branched or unbranched radical, embracing, within the definitions given, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl.
Alkenyl is a branched or unbranched radical, embracing, within the definitions given, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl.
Alkyl which is interrupted by oxygen, sulfur or 
typically embraces, within the definitions given, CH3xe2x80x94Oxe2x80x94CH2xe2x80x94, CH3xe2x80x94Sxe2x80x94CH2xe2x80x94, CH3xe2x80x94NHxe2x80x94CH2xe2x80x94, CH3xe2x80x94N(CH3)xe2x80x94CH2xe2x80x94, CH3xe2x80x94Oxe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2xe2x80x94, CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)2xe2x80x94Oxe2x80x94CH2xe2x80x94, CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)3Oxe2x80x94CH2xe2x80x94 or CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)4Oxe2x80x94CH2xe2x80x94.
C7-C9Phenylalkyl is typically benzyl, xcex1-methylbenzyl, xcex1,xcex1-dimethylbenzyl or 2-phenylethyl. Benzyl and xcex1,xcex1-dimethylbenzyl are preferred.
C1-C4Alkyl-substituted phenyl preferably contains 1 to 3, in particular 1 or 2, alkyl groups is typically o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.
Alkoxy is a branched or unbranched radical, embracing, within the definitions given, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Alkoxy of 1 to 12, in particular of 1 to 8, e.g. of 1 to 6, carbon atoms is preferred.
Alkylene is a branched or unbranched radical, embracing, within the definitions given, methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene. C1-C12Alkylene and, in particular, C2-C8alkylene are preferred.
Alkylene which is interrupted by oxygen, sulfur or 
is within the definitions given, for example, xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94Sxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94NHxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94N(CH3)xe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94Oxe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)2Oxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)3Oxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)4Oxe2x80x94CH2xe2x80x94 or xe2x80x94CH2CH2xe2x80x94Sxe2x80x94CH2CH2xe2x80x94.
Alkenylene, within the definitions given, is typically vinylene, vinylidene, methylvinylene, octenylethylene or dodecenylethylene.
R11 as C1-C12alkyl substituted by a residue benzophenonyl or benzophenonyloxy, wherein one or both phenyl rings of the benzophenone moiety are unsubstituted or substituted by OH, halogen, C1-C4alkyl and/or C1-C18alkoxy, is preferably C1-C12alkyl substituted by a group of the formula XI, XII or XIII 
wherein
the linkage Xxe2x80x2 is a direct bond or xe2x80x94Oxe2x80x94;
X12 is H or OH;
X13 is H, Cl, OH or C1-C18alkoxy;
Xxe2x80x213 is H, Cl or C1-C4alkyl;
X14 is H, Cl, OH or C1-C18alkoxy.
All residues may be straight chain or branched unless otherwise indicated. Hetero atoms are non-carbon atoms, for instance N, O, S or P atoms. Alkyl or alkylene interrupted by hetero groups such as oxygen or cycloalkylene may be interrupted by one or more of these groups as long as no linkages of the type Oxe2x80x94O, Oxe2x80x94N etc. occur.
The compounds of the invention can be pure or mixtures of compounds.
A preferred subject of the invention is, for example, a compound of the formula I, wherein Rw, Rx, Ry and Rz are, independently of each other, C1-C8alkyl, cyclohexyl or C1-C5hydroxyalkyl;
R1 is hydrogen; C1-C8alkyl; oxyl; OH; C1-C18alkoxy; C5-C12cycloalkoxy; C3-C8alkenyl; C3-C8alkynyl; C7-C12phenylalkyl; C7-C15phenylalkoxy; C1-C8alkanoyl; C3-C5alkenoyl; glycidyl; or a group xe2x80x94CH2CH(OH)xe2x80x94G, in which G is hydrogen, methyl or phenyl;
R2 and R6, independently of each other, are hydrogen, C1-C8alkyl, cyclohexyl or C1-C4hydroxyalkyl;
R3, R4, R5, R7, R8, R9, independently of each other, are hydrogen, C1-C8alkyl or cyclohexyl;
when s is 1,
W is C4-C18alkyl; C2-C18alkyl which is substituted by NH2, NHR10, N(R10)2, hydroxy and/or ORxe2x80x213; or W is C5-C12cycloalkyl; cyclohexyl which is substituted by OH, C1-C4alkyl or C1-C4alkoxy; C3-C6alkenyl; C3-C12epoxyalkyl; C7-C15phenylalkyl which is unsubstituted or substituted on the phenyl ring by a radical selected from C1-C4alkyl and C1-C4alkoxy; or W is one of the groups of the formulae (IIa)-(IIe) 
or, when R1 is a group xe2x80x94CH2CH(OH)xe2x80x94G, W may also be hydrogen;
R10 is hydrogen, C1-C8alkyl, C5-C12cycloalkyl, C7-C15phenylalkyl;
R11 is hydrogen; C1-C17alkyl; C1-C12alkyl substituted by OH, C1-C12alkoxy and/or a residue benzophenonyl or benzophenonyloxy, wherein one or both phenyl rings of the benzophenone moiety are unsubstituted or substituted by OH, halogen, C1-C4alkyl and/or C1-C18alkoxy; or R11 is C5-C12cycloalkyl which is unsubstituted or substituted by C1-C4alkyl; C2-C17alkenyl; phenyl; phenyl substituted by NH2, NHR10, N(R10)2, or C1-C4alkyl or C1-C4alkoxy; C7-C15phenylalkyl; or C7-C15phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or C1-C4alkoxy;
R12 is a direct bond or C1-C12alkylene; phenylene; cyclohexylene;
R13 is C1-C18alkyl; C2-C18alkyl which is substituted by NH2, NHR10, N(R10)2, hydroxy and/or OR13; C3-C18alkenyl; C5-C12cycloalkyl; cyclohexyl or oxacyclohexyl which may be substituted by C1-C4alkyl; and when W is a group (IId) and when W is a group (IIb) while R12 is not a direct bond, R13 can be also hydrogen, or one equivalent of a sodium or potassium cation;
Rxe2x80x213 is C1-C18alkyl; C2-C18alkyl which is substituted by NH2, NHR10, N(R10)2, hydroxy and/or OR13; C3-C18alkenyl; C5-C12cycloalkyl; oxacyclohexyl; cyclohexyl which is substituted by C1-C4alkyl;
R14 is C1-C18alkyl; C2-C18alkyl which is substituted by NH2, NHR10, N(R10)2, hydroxy and/or OR13; C5-C12cycloalkyl or oxacyclohexyl each of which is unsubstituted or substituted by C1-C4alkyl; or C7-C15phenylalkyl which is unsubsbtuted or substituted on the phenyl ring by a radical selected from C1-C4alkyl and C1-C4alkoxy;
R15 is a direct bond; C1-C20alkylene; C2-C10alkenylene; C2-C8alkenylene substituted by C6-C12aryl or C6-C12aryl which is substituted by C1-C8alkyl, C1-C8alkoxy, di(C1-C4-alkyl)amino, nitro, thienyl, phenoxyphenyl, phenylthiophenyl, benzo[b]thiophen-2-yl, benzofuran-2-yl, 9H-fluorenyl, biphenylyl, 10H-phenothiazinyl; C2-C4oxaalkylene; C5-C7cycloalkylene; C5-C7cycloalkenylene or phenylene;
when s is 2
W is C2-C12alkylene; C4-C12alkylene substituted by OH and/or interrupted by oxygen or sulfur; C4-C12alkenylene; C6-C12alkenylene substituted by OH and/or interrupted by O; C5-C7cycloalkylene; C5-C7cycloalkylene-di(C1-C4alkylene); C1-C4alkylene-di(C5-C7cycloalkylene); phenylene di(C1-C4alkylene); or one of the groups of the formulae (IIIa)-(IIIe)
xe2x80x94COxe2x80x94R18xe2x80x94COxe2x80x83xe2x80x83(IIIa);
xe2x80x94COOxe2x80x94R19xe2x80x94OOCxe2x80x94xe2x80x83xe2x80x83(IIIb);
xe2x80x94CONHxe2x80x94R20xe2x80x94NHCOxe2x80x94xe2x80x83xe2x80x83(IIIc);
xe2x80x83xe2x80x94(CH2)tCOxe2x80x94xe2x80x83xe2x80x83(IIId);

R18 is a direct bond; C1xe2x80x94C12alkylene; C2-C12alkylene interrupted by oxygen, sulfur and/or xe2x80x94NR10xe2x80x94; C5-C7cycloalkylene; C5-C7cycloalkenylene; or phenylene; C2-C8alkenylene; C2-C8alkenylene substituted by C4-C12aryl or C4-C12aryl which is substituted by C1-C8alkyl, C1-C8alkoxy, di(C1-C4-alkyl)amino; or C2-C8alkenylene substituted by thienyl, phenoxyphenyl, phenylthiophenyl, benzo[b]thiophen-2-yl, benzofuran-2-yl, 9H-fluorenyl, biphenylyl, 10H-phenothiazinyl, thiofuranyl;
R19 is C2-C12alkylene; C4-C12alkylene interrupted by 1, 2 or 3 oxygen atoms; C5-C7cycloalkylene; C5-C7cycloalkylene di(C1-C4alkylene); or C1-C4alkylidene di(C5-C7cycloalkylene);
R20 is C2-C12alkylene; cyclohexylene; phenylene;
Rxe2x80x220 is C2-C12alkylene; cyclohexylene; phenylene; and if i is 1, Rxe2x80x220 additionally embraces methylene;
i is zero or 1;
t is zero or an integer from 1 to 7;
v and z, independently of each other, are an integer from 1 to 4;
when s is 3
W is aliphatic C4-C18triacyl; cycloaliphatic C6-C18triacyl or aromatic C9-C18triacyl; 1,3,5-triazine-2,4,6-triyl; or a group of the formulae (IVa-IVb) 
where R22, R23, R24, independently of each other, are C1-C7alkylene;
when s is 4
W is aliphatic C5-C18tetraacyl; cycloaliphatic C8-C18tetraacyl or aromatic C10-C18tetraacyl or a tetravalent residue of the formula Va
Z1xe2x80x94NR10xe2x80x94R20xe2x80x94NR10xe2x80x94Z2,xe2x80x83xe2x80x83(Va)
wherein Z1 and Z2 are each, independently of one another, a group of the formula Vb, Vc or Vd 
and the group of formula Vb-d is attached via a bond from the triazine ring to the nitrogen atom in formula Va;
when s is 5, W is aliphatic C7-C18pentaacyl; cycloaliphatic C10-C18pentaacyl or aromatic C11-C18pentaacyl;
when s is 6, W is aliphatic C8-C18hexaacyl; cycloaliphatic or aromatic C12-C18hexaacyl or a hexavalent residue of the formula VIa
xe2x80x83Z1xe2x80x94NR10xe2x80x94R20xe2x80x94N(Z2)xe2x80x94R20xe2x80x94NR10xe2x80x94Z3xe2x80x83xe2x80x83(VIa)
wherein Z1, Z2 and Z3, independently of one another, are a group of the formula Vb, Vc or Vd, which is attached via a bond from the triazine ring to the nitrogen atom in formula VIa;
when s is 7, W is aliphatic, cycloaliphatic or aromatic C12-C18heptaacyl;
when s is 8, W is aliphatic, cycloaliphatic or aromatic C12-C18octaacyl or a residue of the formula VIIa
Z1xe2x80x94NR10xe2x80x94R20xe2x80x94N(Z2)xe2x80x94R20xe2x80x94N(Z3)xe2x80x94R20NR10xe2x80x94Z4xe2x80x83xe2x80x83(VIIa)
wherein Z1, Z2, Z3 and Z4 independently of one another, are a group of the formula Vb, Vc or Vd, which is attached via a bond from the triazine ring to the nitrogen atom in formula VIIa; and
Xxe2x80x2 is xe2x80x94Oxe2x80x94 or xe2x80x94N(R10)xe2x80x94.
Also preferred are compounds of the formula (I) wherein p is zero and X is O, thus corresponding to the formula 
Of special importance are the compounds of formula I
where p is zero or 1;
q and r, independently of each other, are an integer from 1 to 6;
s is 1,2,3,4 or 6 or 8;
Rw, Rx, Ry and Rz each are methyl or ethyl;
R1 is hydrogen; C1-C8alkyl; oxyl; OH; C1-C18alkoxy; C5-C12cycloalkoxy; C3-C8alkenyl; C3-C8alkynyl; C7-C12phenylalkyl; C7-C15phenylalkoxy; C1-C8alkanoyl; C3-C5alkenoyl; glycidyl; or a group xe2x80x94CH2CH(OH)xe2x80x94G, in which G is hydrogen, methyl or phenyl;
R2 and R6, independently of each other, are hydrogen, C1-C8alkyl, cyclohexyl or C1-C4hydroxyalkyl;
R3, R4, R5, R7, R8, R9, independently of each other, are hydrogen or methyl;
X is xe2x80x94Oxe2x80x94 or, when p is 1, X is also a group 
where
R10 is hydrogen, C1-C8alkyl, C5-C12cycloalkyl, C7-C15phenylalkyl which is unsubstituted or mono-, di- or tri-substituted or the phenyl by C1-C4alkyl;
when s is 1
W is C1-C18alkyl; C2-C8alkyl which is substituted by NH2, NHR10, N(R10)2; C5-C12cycloalkyl; C3-C6alkenyl; glycidyl; C7-C15phenylalkyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl ring by radicals selected from C1-C4alkyl and C1-C4alkoxy; or W is also a group of the above formula (IIb) or (IId) or a group of the formula (IIxe2x80x2a) or (IIxe2x80x2c): 
or, when R1 is a group xe2x80x94CH2CH(OH)xe2x80x94G, W may also be hydrogen;
R11 is hydrogen; C1-C17alkyl; C5-C12cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by C1-C4alkyl; C2-C17alkenyl; phenyl which is unsubstituted or substituted by NH2, NHR10, N(R10)2 or C1-C4alkyl; C7-C15phenylalkyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl ring by radicals selected from C1-C4alkyl, C1-C4alkoxy;
R12 is a direct bond; C1-C12alkylene;
R13 is C1-C18alkyl; C3-C18alkenyl; C5-C12cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by C1-C4alkyl; and when W is a group (IId), R13 can be also hydrogen, sodium or potassium;
R14 is C1-C18alkyl; C5-C12cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by C1-C4alkyl; or C7-C15phenylalkyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl ring by radicals selected from C1-C4alkyl and C1-C4alkoxy;
R15 is a direct bond; C1-C20alkylene; a group 
a group 
C2-C4oxaalkylene; C5-C7cycloalkylene; C5-C7cycloalkenylene or phenylene;
R16 is C3-C8alkenyl; and
R17 is hydrogen or C1-C8alkyl;
when s is 2
W is C2-C12alkylene; C4-C12alkylene interrupted by 1, 2 or 3 oxygen atoms; C4-C12alkenylene; C5-C7cycloalkylene; C5-C7cycloalkylene di(C1-C4alkylene); C1-C4alkylene di(C5-C7cycloalkylene); C2-C4alkylidene di(C5-C7cycloalkylene); phenylene di(C1-C4alkylene); or one of the groups of the formulae (IIIa)-(IIIe)
xe2x80x94COxe2x80x94R18xe2x80x94COxe2x80x83xe2x80x83(IIIa);
xe2x80x94COOxe2x80x94R19xe2x80x94OOCxe2x80x94xe2x80x83xe2x80x83(IIIb);
xe2x80x94CONHxe2x80x94R20xe2x80x94NHCOxe2x80x94xe2x80x83xe2x80x83(IIIc);
xe2x80x94(CH2)tCOxe2x80x94xe2x80x83xe2x80x83(IIId)

in which R18 is a direct bond; C1-C12alkylene; C2-C12alkylene interrupted by O or S; C2-C8alkenylene; C5-C7cycloalkylene; C5-C7cycloalkenylene; or phenylene; or C2-C8alkenylene substituted by phenyl, naphthyl, thiofuranyl, or phenyl or naphthyl each of which is substituted by C1-C4alkyl or C1-C4alkoxy;
R19 is C2-C12alkylene; C4-C12alkylene interrupted by 1, 2 or 3 oxygen atoms; C5-C7cycloalkylene; C5-C7cycloalkylene di(C1-C4alkylene); or C1-C4alkylidene di(C5-C7cycloalkylene);
R20 and Rxe2x80x220, independently, are C2-C12alkylene; C5-C7cycloalkylene; phenylene;
t is zero or an integer from 1 to 7;
v and z, independently of each other, are an integer from 1 to 4;
when s is 3
W is aliphatic C4-C18triacyl; aromatic C9-C18triacyl or a group of the formula (IVa) or (IVb);
when s is 4
W is aliphatic C6-C18tetraacyl; aromatic C10-C18tetraacyl or a group of the formula (V) 
or a group of the formula (Va);
when s is 6, W is a 1,2,3,4,5,6-cyclohexane hexacarboxy residue or a group of the formula VIa 
when s is 8, W is a residue of the formula VIIa 
Other compounds of the formula I of special interest are those of the formula Ixe2x80x3
wherein
Rw, Rx, Ry and Rz are, independently of each other, C1-C18alkyl, C5-C12cycloalkyl or C1-C5hydroxyalkyl, especially methyl;
R1 is hydrogen; C1-C18alkyl; oxyl; OH; CH2CN; C1-C18alkoxy; C5-C12cycloalkoxy; C3-C8alkenyl; C3-C8alkynyl; C7-C12phenylalkyl; C7-C15phenylalkyl, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C1-C4alkyl and C1-C4alkoxy; C7-C15phenylalkoxy; C7-C15phenylalkoxy, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C1-C4alkyl and C1-C4alkoxy; or R1 is C1-C8alkanoyl; C3-C5alkenoyl; C1-C18alkanoyloxy; glycidyl; or a group xe2x80x94CH2CH(OH)xe2x80x94G, in which G is hydrogen, methyl or phenyl;
R2, R3, R4, R5, R6, R7, R8, R9, independently of each other, are hydrogen, C1-C8alkyl or C5-C12cycloalkyl;
p is zero or 1;
q and r, independently of each other, are integers from 1 to 6;
X is as defined for formula I and
R25 is phenyl which is unsubstituted or mono-, di- or tri-substituted by C1-C8alkyl, C1-C8alkoxy, di(C1-C4-alkyl)amino, nitro; or is phenyl which is mono- or di-substituted by a group of the formula (IIxe2x80x3) 
in which Rw, Rx, Ry, Rz, R1, R2, R3, R4, R5, R6, R7, R8, R9, X, p, q, r are as defined above; or R25 is naphtyl which is unsubstituted or mono-substituted by C1-C4alkyl, C1-C4alkoxy, di(C1-C4-alkyl)amino or nitro; or R25 is thienyl, phenoxyphenyl, phenylthiophenyl, benzothiophenyl, benzofuranyl, 9H-fluorenyl, biphenylyl, 10H-phenothiazinyl.
More preferred compounds are of the formula Ixe2x80x2
wherein
q is 1 or 2; and s is a number 1, 2, 3, 4, 6 or 8;
Rw, Rx, Ry and Rz are, independently of each other, methyl or ethyl;
R1 is hydrogen; C1-C4alkyl; C3-C12alkoxy; cyclohexyloxy; acetyl; C3-C5alkenoyl; or R1 is glycidyl or a group xe2x80x94CH2CH(OH)xe2x80x94G, in which G is hydrogen or methyl;
R2, R3, R4, R5 independently of each other are hydrogen or methyl;
when s is 1,
W is C6-C18alkyl; cyclohexyl; C2-C8alkyl which is substituted by NH2, NHR10, N(R10)2; or W is glycidyl; or W is a group of the formula (IIa) 
or, when R1 is a group xe2x80x94CH2CH(OH)xe2x80x94G, W may also be hydrogen;
R10 is hydrogen, C1-C8alkyl, cyclohexyl;
R11 is C1-C17alkyl; cyclohexyl; phenyl; phenyl substituted by NH2, NHR10, N(R10)2;
R12 is a direct bond;
when s is 2,
W is C2-C12alkylene; C4-C12alkylene interrupted by sulfur; or a group of the formula (IIIa):
COxe2x80x94R18xe2x80x94COxe2x80x83xe2x80x83(IIIa);
R18 is C1-C12alkylene; C4-C12alkylene interrupted by O or S or NR10; phenylene; cyclohexylene; C2-C8alkenylene; C2-C8alkenylene substituted by a group 
or by phenyl or naphthyl, or by phenyl or naphthyl, each of which is substituted by methyl or methoxy;
when s is 3,
W is 1,3,5-triazine-2,4,6-triyl; or a group of the formula IVb 
Rxe2x80x220 is C2-C8alkylene or phenylene;
i is zero or 1;
when s is 4,
W is a residue of the formula Ve or Vf 
R20 is C2-C8alkylene;
when s is 6,
W is cyclohexane hexaacyl or a residue of the formula VIa 
when s is 8,
W is a residue of the formula VIIa 
Some of the above compounds of the formula I are especially well suitable for the preparation of polymeric light stabilizers or for grafting them onto organic polymers having suitable functional groups. These are mainly compounds of the formula I carrying a hydroxy or epoxy group or a polymerizable ethylenic double bond.
The invention therefore also pertains to a process for grafting a compound of the formula I carrying a hydroxy or epoxy group or a polymerizable ethylenic double bond onto an onto organic polymer carrying suitable functional groups.
Compounds of the formula I suitable for grafting and carrying a hydroxy group are preferably compounds of the formula I, wherein s is 1 and W is hydroxyalkyl or hydrogen or wherein s is 1 and R2 is hydroxyalkyl, or a precursor compound for compounds of the formula I such as a compound of formula IX or of examples 1-5 below. Polymers having suitable functional groups for the reaction with these hydroxy compounds are mainly organic polymers containing carboxy, anhydride or epoxy groups.
Compounds of the formula I suitable for grafting and carrying an epoxy group are preferably compounds of the formula I, wherein s is 1 and W is C3-C12epoxyalkyl, especially glycidyl. Polymers having suitable functional groups for the reaction with these epoxy compounds are mainly organic polymers containing carboxy and/or hydroxy groups.
Compounds of the formula I suitable for grafting and carrying an ethylenic double bond are preferably compounds of the formula I, wherein R1 is acryloyl or methacryloyl; or wherein s is 1, W is a group of the formula (IIa) with R12 being a direct bond and R11 being 1-alkenyl or W is a group of the formula (IId) with R15 being alkenylene or substituted alkenylene with the ethylenic double bond vicinal to Cxe2x95x90O; or wherein s is 2 and W is a group of the formula (IIIa) with R18 being alkenylene or substituted alkenylene with the ethylenic double bond vicinal to Cxe2x95x90O.
Grafting reactions can be carried out in close analogy to methods known in the art, e.g. to methods described in EP-A-526399, pages 6-16, or to methods described in U.S. Pat. No. 5,189,084, see especially column 6, line 59, until column 7, line 53, and example 1; these passages of U.S. Pat. No. 5,189,084 are hereby incorporated by reference. Polymers thus modified and containing a high amount of units of formula I or IX, e.g. 5 to 90, especially 10 to 80% by weight of the modified polymer, can be used as stabilizers for organic material in the same manner as described for compounds of the formula I.
The invention further pertains to a process for the polymerization or copolymerization of a compound of the formula I carrying an epoxy group or a polymerizable ethylenic double bond or 2 hydroxy groups within the same molecule.
(Co)polymerization reactions can be carried out in close analogy to methods known in the art, e.g. to methods described in U.S. Pat. No. 5,189,084, column 5, lines 10-52, and references cited therein, as well as example 2 of U.S. Pat. Nos. 5,189,084; 5,521,282 or 5,710,240. The cited passages of U.S. Pat. No. 5,189,084 are hereby incorporated by reference.
Compounds of the formula I suitable for polymerization and carrying an ethylenic double bond are preferably compounds of the formula 1, wherein s is 1, W is a group of the formula (IIa) with R12 being a direct bond and R11 being 1-alkenyl or W is a group of the formula (IId) with R15 being alkenylene or substituted alkenylene with the ethylenic double bond vicinal to Cxe2x95x90O; or wherein s is 2 and W is a group of the formula (IIIa) with R 18 being alkenylene or substituted alkenylene with the ethylenic double bond vicinal to Cxe2x95x90O; or wherein s is 1 and R1 is acryloyl or methacryloyl. These compounds may be reacted in close analogy to methods known in the art to obtain homopolymers or, by reacting with a further ethylenically unsaturated monomer, to obtain copolymers.
Compounds of the formula I suitable for polymerization and carrying an epoxy group are preferably compounds of the formula I, wherein s is 1 and R1 is glycidyl or W is C3-C12epoxyalkyl, especially glycidyl. Preferably, these compounds are reacted to polyethers following the method described in U.S. Pat. No. 5,521,282, column 4, line 16, until column 5, line 19; this passage of U.S. Pat. No. 5,521,282 is hereby incorporated by reference.
Compounds of the formula I suitable for polymerization and 2 hydroxy groups are preferably compounds of the formula I, wherein s is 1 and two of the residues W, R2 and R1 contain a hydroxy group or, as it is preferred, R1 is a group of formula xe2x80x94CH2CH(OH)xe2x80x94G and R2 is either hydroxyalkyl while W is alkyl or R2 is hydrogen or alkyl and W is hydrogen.
Preferably, these compounds are reacted with a suitable derivative of a dicarboxylic acid to obtain a polyester according to methods known in the art; the reaction can, for example, follow one of the methods described in U.S. Pat. No. 5,710,240.
Preferred is a polymer containing tetramethylpiperazinone side chains and comprising from 1-100 mol % of recurring units of the formula L 
and 0-99 mol % of recurring units of the formula LI
xe2x80x94(xe2x80x94CH2xe2x80x94C(R27)(R28)xe2x80x94A1xe2x80x94)xe2x80x94xe2x80x83xe2x80x83(LI)
wherein
TMPZ is a tetramethylpiperazinone side chain of the formula 
with R1 being H; C1-C4alkyl; C3-C12alkoxy; cyclohexyloxy; acetyl; R2, R3, R4 and R5 independently being H or methyl; W being C1-C18alkyl; cyclohexyl; or a group xe2x80x94COxe2x80x94R11, where R11 is C1-C17alkyl; cyclohexyl; phenyl; and q is as defined above;
A1 is oxygen or a direct bond;
when A1 is oxygen,
A2 is CH2,
R26 and R27 each are H, and
R28 is C1-C18alkyl, C1-C18alkoxy, C1-C12alkoxymethyl; C5-C9cycloalkyl, cyclohexyloxy, phenyl, C7-C9phenylalkyl, or hydrogen;
when A1 is a direct bond,
A2 is CO,
R26 and R27 independently are H or methyl, and
R28 is COOH, CONH2, or COOR29, where R29 is C1-C12alkyl or C1-C8hydroxyalkyl.
Preferred are homopolymers consisting of recurring units of formula L.
Also preferred is a polymer comprising recurring units of the formula LIV 
wherein
R2, R3, R4 and R5 independently are H or methyl;
G is H, methyl or phenyl;
q is a number ranging from 1 to 6, preferably 1 or 2;
A3 is a direct bond; C1-C12alkylene; C2-C12alkylene interrupted by S, NR10 or O, where R10 as defined above for formula I; cyclohexylene or phenylene; especially C1-C12alkylene or phenylene.
Polymers of formula LIV and polymers containing structural units of formula L usually have a molecular weight Mn measured by gel permeation chromatography from 600 to 600000 g/mol; preferably Mn is 1000-30000 g/mol, especially 1000-10000 g/mol. The polymeric compounds of the invention can be employed as stabilizers for organic material against effects of light, oxygen and/or heat in the same manner as described for the compounds of formula I.
End groups of the polymers of the invention are determined by the preparation process described; usually end groups are H, OH or C1-C6alkyl; in case of formula LIV, end groups may be also 
where R, independently, is H or C1-C6alkyl.
The preparation of compounds of the formula I can start from free alcohol precursors corresponding to formula IX 
wherein R1 is hydrogen or C1-C4alkyl and the other symbols are as defined for formula I. Some specific compounds of this class are known; prior art describes their synthesis using phase transfer catalysis and/or cyanide or cyanhydrine. In particular, suitable 1,2-diamine derivatives are reacted with a saturated ketone and a haloform reactant (represented for 2-oxo-3,3,5,5-tetramethyl piperazine compounds by acetone and chloroform respectively) in an organic solvent for the reactants (represented in the prior art mostly by methylenechloride), in the presence of aqueous alkali and ammonium salts, such as tetraalkyl ammonium halide, following the usual phase transfer catalysis (PTC) conditions (see U.S. Pat. Nos. 4,167,512, 4,190,571, 4,246,412, 4,297,492, 4,466,915, 4,698,446 and J. Lai, Synthesis 1981, 40-41).
The following useful precursor compounds embraced by the formula (IX) are new and are also subject of present invention:
1-(2-hydroxyethyl)-3,3,5,5-tetramethyl-piperazin-2-one,
1-(2-hydroxyethyl)-3,3,4,5,5-pentamethyl-piperazin-2-one,
1-(2-hydroxypropyl)-3,3,5,5-tetramethyl-piperazin-2-one,
1-(2-hydroxypropyl)-3,3,4,5,5-pentamethyl-piperazin-2-one.
The precursor compounds of the formula (IX) also can be employed as stabilizers for organic materials. Of special value is their use as stabilizers for photographic material.
Compounds of the formula (IX) may be reacted to compounds of the formula (I), e.g. wherein R1 is other than hydrogen or lower alkyl and/or s is other than 1, using methods known in the art; examples for such methods are alkylation, (trans)esterification or etherification, substitution etc.
In an improved process, a 1,1-dimethyl-1,2-ethylenediamine is reacted with chloroform and acetone as described in prior art for the ketoform reaction, but acetone is used as a solvent as well as a reactant, the amount of chloroform is in slight molar excess over the amount of diamine, for example between 1 and 2 moles CHCl3 per mole of diamine, and alkaline hydroxide, preferably sodiumhydroxide, is used in large excess over the diamine, e.g. 3-10 moles per mol diamine. In particular, the molar ratio CHCl3:diamine:alkali hydroxide in the improved process is preferably from 1.1:1:4.4 to 1.5:1:6, thus providing an excellent regioselectivity control. The resulting regioisomer ratio of products of the type (A):(B) is typically 95:1 or higher, (A) being the desired product. Products are obtained in good yields. Alkaline hydroxide, especially sodium hydroxide, is preferably used in concentrated aqueous solution, e.g. containing 50% by weight NaOH.
By using the above mentioned conditions, an excellent regioselectivity control is obtained so that no separation is needed. As a further advantage, the reaction proceeds in one phase thus avoiding phase transfer catalysis. The reaction is carried out at temperature xe2x88x9220xc2x0 C. to 60xc2x0 C.; a temperature 0xc2x0 C. to 25xc2x0 C. is preferred.
Compounds thus obtained may be further derivatized by applying suitable synthetic methods known in the art, e.g. in analogy to methods described in EP-A-375612, U.S. Pat. Nos. 5,204,473, 5,004,770, and Kurumada et al., J. Polym. Sci., Poly. Chem. Ed. 23, 1477 (1985), as well as U.S. Pat. No. 5,449,776, example 8, and publications cited therein, for the modification of piperidine derivatives.
The diamine intermediates can be prepared by using a Mannich reaction among formaldehyde or paraformaldehyde, the suitable alkanolamine as a starting material and 2-nitropropane, followed by hydrogenation to reduce the nitro group to amine group in the presence of a suitable catalyst such as Raney-Ni. This reaction can be carried out according to known methods, for instance as described in U.S. Pat. No. 4,698,446 (column 10 lines 10-13) or in analogy to those methods.
All in the various steps indicated for all the reactions may be carried out in a single reactor or in the same reaction medium without isolating the intermediate compounds or may be carried out after separation and, where appropriate, purification.
Compounds of the formula (Ixe2x80x3) can be prepared by reaction of the appropriate molar amounts of a compound of the formula (IIIxe2x80x3) 
or on its derivatives such as C1-C4alkyl diester or its acid halide, e.g. dichloride, with the appropriate molar amounts of a compound of the formula (IVxe2x80x3) 
where R1, R2, R3, R4, R5, R6, R7, R8, R9, X, p, q, r are as defined above, at temperature 80xc2x0 C. to 200xc2x0 C., preferably 120xc2x0 C.-180xc2x0 C. in neat or in an inert solvent such as toluene, xylene, trimethylbenzene, dimethylformamide, dimethylacetamide. Xylene is preferred.
When C1-C4alkyl ester derivative of the compound of the formula (IIIxe2x80x3) is used, the reaction can be carried out in neat or in an inert solvent such as toluene, xylene, trimethylbenzene; xylene is preferred; preferably the reaction is carried out in the presence of a transesterification catalyst, such as alkali metals, their hydrides, amides or alcoholates, titanium (IV) alkoxide or dialkyl tin (IV) oxide; sodium alcoholate or dibutyl tin (IV) oxide being preferred.
When an acyl halide of the compound of the formula (III) is used, the reaction may be carried out in an inert solvent such as toluene, xylene, trimethylbenzene, dichloroethane; xylene being preferred; in the presence of an inorganic or organic base such as tri(C2-C4alkyl)amines, sodium hydroxide, sodium carbonate, potassium hydroxyide, potassium carbonate, an inorganic base such as, for example, sodium hydroxide or sodium carbonate being preferred.
Compounds of the formula IIIxe2x80x3 are known or may be made from known compounds by known methods or in close analogy to those methods.
Compounds of the formula IVxe2x80x3 can be prepared according to the reaction scheme hereunder reported: 
where R2, R3, R4, R5, R6, R7, R8, R9, p, q and r are as defined above. 
Reaction conditions thereby are kept closely to the descriptions given in prior art or follow the improved process described above. Compounds of the formula (Ixe2x80x3) wherein X is a group xe2x80x94N(R10)xe2x80x94, where R10 is as defined above, can be obtained in analogy to the above procedure or by processing the above product in a known manner or by applying analogous methods.
The novel compounds of present invention can be employed with advantage for stabilizing organic material against the damaging effect of light, oxygen and/or heat. They are notable for high substrate compatibility and good persistence in the substrate.
Examples of materials to be stabilized in accordance with the invention are:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbonene, polyethyl ene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerisation (normally under high pressure and at elevated temperature).
b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either xcfx80- or xcfx84-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propyleneisobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(xcex1-methylstyrene).
6. Copolymers of styrene or xcex1-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/ styrene.
7. Graft copolymers of styrene or xcex1-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloridevinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from xcex1,xcex2-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PANPP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
The invention therefore also provides compositions comprising
A) an organic material which is sensitive to oxidative, thermal and/or actinic degradation, and
B) at least one compound of the formula I, and provides for the use of compounds of the formula I for stabilizing organic material against oxidative, thermal or actinic degradation.
Effects of degradation inter alia may be discoloration, molecular breakdown or buildup.
Thus, the invention likewise embraces a method of stabilizing organic material against thermal, oxidative and/or actinic breakdown/buildup, which comprises applying or adding at least one compound of the formula I to this material.
Of particular interest is the use of compounds of the formula I as stabilizers in synthetic organic polymers, especially thermoplastic polymers, and corresponding compositions, in film forming binders for coatings and in reprographic material.
The organic materials to be protected are preferably natural, semisynthetic or, preferably, synthetic organic materials. Particular preference is given to synthetic organic polymers or mixtures of such polymers, especially thermoplastic polymers such as polyolefins, especially polyethylene and polypropylene (PP), and coating compositions. Of special importance are also polycarbonates and blends thereof, such as a blend of polycarbonate and a second polymer selected from the group consisting of the polyesters, styrenic copolymers, rubbers and vinyl chloride polymers or copolymers; further examples are the polymers listed above under items 19 and 28. The second polymer in the polycarbonate blend is preferably selected from the group consisting acrylonitrile-butadiene-stryene (ABS resin), acrylonitrile-styrene-acrylate (ASA resin), acrylonitrile-EPDM-styrene (AES resin), styrene-acrylonitrile (SAN resin), poly(ethylene terephthalate), poly(butylene terephthalate), methyl methacrylate-butadiene-styrene (MBS resin), acrylic rubber, nitrile rubber, polybutadiene, polyisoprene, poly(vinyl chloride) and ABS resin; and poly(vinyl chloride) and ASA resin; preferably ABS resin.
In general the compounds of the formula I are added to the material to be stabilized in amounts of from 0.1 to 10%, preferably from 0.01 to 5%, in particular from 0.01 to 2% (based on the material to be stabilized). Particular preference is given to the use of the novel compounds in amounts of from 0.05 to 1.5%, especially from 0.1 to 0.5%.
Incorporation into the materials can be effected, for example, by mixing in or applying the compounds of the formula I and, if desired, further additives by the methods which are customary in the art. Where polymers are involved, especially synthetic polymers, incorporation can take place prior to or during the shaping operation, or by applying the dissolved or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices. A further possibility for incorporating the compounds of the formula I into polymers is to add them before, during or directly after the polymerization of the corresponding monomers or prior to crosslinking. In this context the compound of the formula can be added as it is or else in encapsulated form (for example in waxes, oils or polymers). In the case of addition prior to or during the polymerization, the compounds of the formula I can also act as a regulator of the chain length of the polymers (chain terminator).
The compounds of the formula I can also be added in the form of a masterbatch containing said compound in a concentration, for example, of from 2.5 to 25% by weight to the polymers that are to be stabilized.
The compounds of the formula I can judiciously be incorporated by the following methods:
as emulsion or dispersion (e.g. to latices or emulsion polymers),
as a dry mixture during the mixing in of additional components or polymer mixtures,
by direct introduction into the processing apparatus (e.g. extruders, internal mixers, etc),
as solution or melt.
Novel polymer compositions can be employed in various forms and/or processed to give various products, for example as (to give) films, fibres, tapes, moulding compositions, profiles, or as binders for coating materials, adhesives or putties.
Other materials to be stabilized with the novel compositions are recording materials. By such materials are meant, for example, those described in Research Disclosure 1990, 31429 (pages 474-480), or in GB-A-2319523 or DE-A-19750906, page 22, line 15, until page 105, line 32, for photographic reproduction and other reprographic techniques.
Of special importance is the stabilization of non-silver reprographic materials, for example, those for pressure-sensitive copying systems, microcapsule photocopier systems, heat-sensitive copier systems and ink-jet printing.
The novel recording materials feature an unexpectedly high quality, especially in terms of their light stability.
The novel recording materials have a structure which is known per se and which corresponds to the utility. They consist of a base, for example paper or plastic film, on which one or more coatings are applied. Depending on the type of material, these coats contain the suitable components required, in the case of photographic material for example silver halide emulsions, colour couplers, dyes and the like. The material intended especially for ink-jet printing has a customary base on which there is an absorption layer suitable for ink. Uncoated paper can likewise be employed for ink-jet printing; in this case, the paper functions simultaneously as a base and has the absorbent for the ink. Suitable material for ink-jet printing is described, inter alia, in U.S. Pat. No. 5,073,448, the disclosure content of which is regarded as part of the present description.
The recording material can also be transparent, for example in the case of projection films.
The compound or compounds of the formula I can be incorprated into the material even in the course of manufacture; in papermaking, for example, by addition to the pulp. Another method of use is the spraying of the material with an aqueous solution of compound(s) of the formula I, or the addition thereof to the coating.
Coatings for transparent recording materials for projection must not contain any light-scattering particles such as pigments or fillers.
The colour-binding coatings can contain further additives, for example antioxidants, light stabilizers (including UV absorbers or hindered amine light stabilizers which are not included among the novel compounds of formula I), viscosity improvers, brighteners, biocides and/or antistats.
The coating is usually prepared as follows:
The water-soluble components, for example the binder, are dissolved in water and mixed. The solid components, for example fillers and other additives as already described, are dispersed in this aqueous medium. Dispersion is advantageously brought about with the aid of equipment such as ultrasonic devices, turbine agitators, homogenizers, colloid mills, bead mills, sand mills, high-speed stirrers and the like. A particular advantage of the compounds of the formula I is their ease of incorporation into the coating.
As mentioned, the novel recording materials cover a broad field of use. Compounds of the formula I can be employed, for example, in pressure-sensitive copier systems. They can be added to the paper to protect the microencapsulated dye precursors against light, or to the binder of the developer layer for protecting the dyes formed therein.
Photocopier systems with light-sensitive microcapsules which are developed by pressure are described, inter alia, in U.S. Pat. Nos. 4,416,966; 4,483,912; 4,352,200; 4,535,050; 45,365,463; 4,551,407; 4,562,137 and 4,608,330; and also in EP-A-139479; EP-A-162664; EP-A-164931; EP-A-237024; EP-A-237025 and EP-A-260129. In all these systems the compounds of the formula I can be added to the colour-accepting layer. Alternatively, the compounds of the formula I can be added to the donor layer for protecting the colour formers against light.
The compounds of the formula I can also be employed in recording materials which are based on the principle of photopolymerization, photosoftening or the rupture of microcapsules, or when heat-sensitive or photosensitive diazonium salts, leuco dyes with oxidizing agent or colour lactones with Lewis acids are used.
Heat-sensitive recording material exploits the colour-imparting reaction between a colourless or weakly coloured base dye and an organic or inorganic colour developer, the recorded image being produced by heat-induced contact of the two materials. This type of heat-sensitive recording material is very widespread, not only as the recording medium for faxes, computers, etc., but also in many other fields, for example in label printing.
The heat-sensitive recording material according to the present invention is composed of a base, a heat-sensitive colour-forming recording layer on this base, and, optionally, a protective layer on the heat-sensitive, colour-forming recording layer. The heat-sensitive, colour-forming recording layer contains as its principal constituent a colour-imparting compound and a colour-developing compound, and also a compound of the formula I. If the said protective layer is present, the compound of the formula I can also be incorporated into the protective layer.
Heat-sensitive recording materials are described, for example, in JP-A8-267 915.
Further fields of use are recording materials for dye diffusion transfer printing, thermal wax transfer printing and dot matrix printing, and for use with electrostatic, electrographic, electrophoretic, magnetographic and laser-electrophotographic printers, recorders or plotters. Of the materials mentioned, preference is given to recording materials for dye diffusion transfer printing, as are described, for example, in EP-A-507,734.
Compounds of the formula I can also be employed in inks, preferably for ink-jet printing, for example those as described in U.S. Pat. No. 5,098,477, the disclosure content of which is regarded as part of the present description. The invention therefore also provides an ink comprising at least one compound of the formula I as stabilizer. The ink, especially for ink-jet printing, contains preferably water. Inks contain the stabilizer of the formula I usually in a concentration of from 0.01 to 20% by weight, in particular from 0.5 to 10% by weight.
The novel photographic material can be a black and white or a colour photographic material; colour photographic material is preferred.
Examples of colour photographic materials are colour negative films, colour reversal films, colour positive films, colour photographic paper, colour reversal photographic paper, colour-sensitive materials for the dye diffusion transfer process or the silver dye bleach process.
In general, the compounds of the formula I are contained in the photographic material in an amount from 10 to 1000 mg/m2, especially from 30 to 500 mg/m2.
The compounds of the invention can be incorporated in any layer of a silver halide photographic material, however, they are preferentially incorporated in a chromogenic layer, more preferentially in a layer containing a yellow coupler. They are preferentially used in a 1% to 200% weight ratio with the coupler, more preferentially 1% to 100%. Compounds of present invention show a high efficacy as stabilizers for the dye, especially the yellow dye, in the photographic material.
Yellow couplers which can be used in the novel material are preferably compounds of the formula A 
in which R1 is alkyl, cycloalkyl, arylamino, anilino, a heterocyclic group or aryl, R2 is aryl and Q is hydrogen or a group which can be eliminated by reaction with the oxidized developer.
The compounds of the present invention can be used in combination with other stabilisers that can be incorporated in the same layer or in a different layer. Possible stabiliser include phenolic stabilisers, conventional HALS or UV absorbers of the hydroxyphenyl benztriazole type or of the hydroxyphenyl triazine class such as described inter alia in GB-A-2319523, DE-A-19750906; see also items 1.1, 2.1, 2.6, 2.8 of the list following below. Special preference is given to a combination with a UV absorber corresponding to the formula 
wherein R1 is an organic residue, e.g. an alkyl group, and the residues R are independently of each other H or organic substituents; compounds of this class are disclosed in GB-A-2319523 and DE-A-19750906.
Details of the photographic material to be stabilized according to the invention and components which can be employed in the novel material are given, inter alia, in GB-A-2319523, DE-A-19750906, page 23, line 20, until page 105, line 32, and in U.S. Pat. No. 5,538,840, column 25, line 60, to column 106, line 31; these parts of U.S. Pat. No. 5,538,840 are incorporated herein by way of reference. Further important components, especially couplers, are described in U.S. Pat. No. 5,578,437.
In addition to the compounds of the formula I, the novel compositions may as additional component C comprise one or more conventional additives such as, for example, those indicated below.
1. Antioxidants
1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(xcex1-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1xe2x80x2-methylundec-1xe2x80x2-yl)phenol, 2,4-dimethyl-6-(1xe2x80x2-methylheptadec-1xe2x80x2-yl)phenol, 2,4-dimethyl-6-(1xe2x80x2-methyltridec-1xe2x80x2-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.
1.4. Tocopherols, for example xcex1-tocopherol, xcex2-tocopherol, xcex3-tocopherol, xcex4-tocopherol and mixtures thereof (Vitamin E).
1.5. Hydroxylated thiodiphenyl ethers, for example 2,2xe2x80x2-thiobis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-thiobis(4-octylphenol), 4,4xe2x80x2-thiobis(6-tert-butyl-3-methylphenol), 4,4xe2x80x2-thiobis(6-tert-2-methylphenol), 4,4xe2x80x2-thiobis-(3,6-di-sec-amylphenol), 4,4xe2x80x2-bis(2,6-dimethyl-4-hydroxyphenyl)sulfide.
1.6. Alkylidenebisphenols, for example 2,2xe2x80x2-methylenebis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-methylenebis(6-tert-butyl-4-ethylphenol), 2,2xe2x80x2-methylenebis[4-methyl-6-(xcex1-methylcyclohexyl)-phenol], 2,2xe2x80x2-methylenebis(4-methyl-6-cyclohexylphenol), 2,2xe2x80x2-methylenebis(6-nonyl-4-methylphenol), 2,2xe2x80x2-methylenebis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidenebis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2xe2x80x2-methylenebis[6-(xcex1-methylbenzyl)-4-nonylphenol], 2,2xe2x80x2-methylenebis[6-(xcex1,xcex1-dimethylbenzyl)-4-nonylphenol], 4,4xe2x80x2-methylenebis(2,6-di-tert-butylphenol), 4,4xe2x80x2-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3xe2x80x2-tert-butyl-4xe2x80x2-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
1.7. O-, N- and S-benzyl compounds, for example 3,5,3xe2x80x2,5xe2x80x2-tetra-tert-butyl-4,4xe2x80x2-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, didodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of xcex2-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.15. Esters of xcex2-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,Nxe2x80x2-bis(3,5-di-tert-butyl-hydroxyphenylpropionyl)trimethylenediamide, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazide, N,Nxe2x80x2-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard(copyright)XL-1 supplied by Uniroyal).
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants, for example N,Nxe2x80x2-di-isopropyl-p-phenylenediamine, N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, N,Nxe2x80x2-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-methylheptyl)-p-phenylenediamine, N,Nxe2x80x2-dicyclohexyl-p-phenylenediamine, N,Nxe2x80x2-diphenyl-p-phenylenediamine, N,Nxe2x80x2-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1-methylheptyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-cyclohexyl-Nxe2x80x2-phenyl-p-phenlenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,Nxe2x80x2-dimethyl-N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,pxe2x80x2-di-tert-octyidiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4xe2x80x2-diaminodiphenylmethane, 4,4xe2x80x2-diaminodiphenylmethane, N,N,Nxe2x80x2,Nxe2x80x2-tetramethyl-4,4xe2x80x2-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1xe2x80x2,3xe2x80x2-dimethylbutyl)phenyl]amine, tertoctylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tertoctyldiphenylamines, a mixture of mono- and dialkylated nonydiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylated tert-butydiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- und dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylated tert-octyl-phenothiazines, N-allylphenothiazin, N,N,Nxe2x80x2,Nxe2x80x2-tetraphenyl-1,4-diaminobut-2-ene, N,Nxe2x80x2-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
2. UV absorbers and light stabilisers
2.1. 2-(2xe2x80x2-Hydroxyphenyl)benzotriazoles, for example 2-(2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)-benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(5xe2x80x2-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(2xe2x80x2-hydroxy-5xe2x80x2-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-butyl-2xe2x80x2-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-sec-butyl-5xe2x80x2-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(2xe2x80x2-hydroxy-4xe2x80x2-octyloxyphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-amyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-bis-(xcex1,xcex1-dimethylbenzyl)-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-5xe2x80x2-[2-(2-ethylhexyloxy)-carbonylethyl]-2xe2x80x2-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-5xe2x80x2-[2-(2-ethylhexyloxy)carbonylethyl]-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2-dodecyl-2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2xe2x80x2-methylene-bis-[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3xe2x80x2-tert-butyl-5xe2x80x2-(2-methoxycarbonylethyl)-2xe2x80x2-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [Rxe2x80x94CH2CH2xe2x80x94COOxe2x80x94CH2CH2"Brketclosest"2 where R=3xe2x80x2-tert-butyl-4xe2x80x2-hydroxy-5xe2x80x2-2H-benzotriazol-2-ylphenyl, 2-[2xe2x80x2-hydroxy-3xe2x80x2-(xcex1,xcex1-dimethylbenzyl)-5xe2x80x2-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole; 2-[2xe2x80x2-hydroxy-3xe2x80x2-(1,1,3,3-tetramethylbutyl)-5xe2x80x2-(xcex1,xcex1-dimethylbenzyl)-phenyl]benzotriazole.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2xe2x80x2,4xe2x80x2-trihydroxy and 2xe2x80x2-hydroxy-4,4xe2x80x2-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates, for example ethyl xcex1-cyano-xcex2,xcex2-diphenylacrylate, isooctyl xcex1-cyano-xcex2,xcex2-diphenylacrylate, methyl xcex1-carbomethoxycinnamate, methyl xcex1-cyano-xcex2-methyl-p-methoxy-cinnamate, butyl xcex1-cyano-xcex2-methyl-p-methoxy-cinnamate, methyl xcex1-carbomethoxy-p-methoxycinnamate and N-(xcex2-carbomethoxy-xcex2-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2xe2x80x2-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyidithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tertbutylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, 1,1xe2x80x2-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cyclic condensates of N,Nxe2x80x2-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane und epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,Nxe2x80x2-bis-formyl-N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diester of 4-methoxymethylene-malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, reaction product of maleic acid anhydride-xcex1-olefin-copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.
2.7. Oxamides, for example 4,4xe2x80x2-dioctyloxyoxanilide, 2,2xe2x80x2-diethoxyoxanilide, 2,2xe2x80x2-dioctyloxy-5,5xe2x80x2-di-tert-butoxanilide, 2,2xe2x80x2-didodecyloxy-5,5xe2x80x2-di-tert-butoxanilide, 2-ethoxy-2xe2x80x2-ethyloxanilide, N,Nxe2x80x2-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2xe2x80x2-ethoxanilide and its mixture with 2-ethoxy-2xe2x80x2-ethyl-5,4xe2x80x2-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
3. Metal deactivators, for example N,Nxe2x80x2-diphenyloxamide, N-salicylal-Nxe2x80x2-salicyloyl hydrazine, N,Nxe2x80x2-bis(salicyloyl)hydrazine, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,Nxe2x80x2-diacetyladipoyl dihydrazide, N,Nxe2x80x2-bis(salicyloyl)oxalyl dihydrazide, N,Nxe2x80x2-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4xe2x80x2-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 2,2xe2x80x2,2xe2x80x3-nitrilo[triethyltris(3,3xe2x80x2,5,5xe2x80x2-tetra-tert-butyl-1,1xe2x80x2-biphenyl-2,2xe2x80x2-diyl)phosphite], 2-ethylhexyl(3,3xe2x80x2,5,5xe2x80x2-tetra-tert-butyl-1,1xe2x80x2-biphenyl-2,2xe2x80x2-di-yl)phosphite.
Especially preferred are the following phosphites:
Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos(copyright)168, Ciba-Geigy), tris(nonylphenyl)phosphite, 
5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
7. Thiosynergists, for example, dilauryl thiodipropionate or distearyl thiodipropionate.
8. Peroxide scavengers, for example esters of xcex2-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyidithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(xcex2-dodecylmercapto)propionate.
9. Polyamide stabilisers, for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zink pyrocatecholate.
11. Nucleating agents, for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers).
12. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
13. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
14. Benzofuranones and indolinones, for example those disclosed in U.S. Pat. Nos. 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-591102 or 3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3xe2x80x2-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
The conventional additives are judiciously employed in amounts of 0.1-10% by weight, for example 0.2-5% by weight, based on the material to be stabilized.
Costabilizers optionally to be added to the stabilizer mixture of the invention are preferably further light stabilizers, for instance those of the 2-hydroxyphenyl-benztriazole, 2-hydroxyphenyl-triazine, benzophenone or oxalanilide classes, e.g. as described in EP-A-453396, EP-A-434608, U.S. Pat. No. 5,298,067, WO 94/18278, GB-A-2297091 and WO 96/28431, and/or further hindered amines derived from 2,2,6,6-tetraalkylpiperidine containing at least one group of the formula 
in which G is hydrogen or methyl, especially hydrogen; examples of tetraalkylpiperidine derivatives which can be used as costabilizers with mixtures of the invention are given in EP-A-356 677, pages 3-17, sections a) to f). These sections of this EP-A are regarded as part of the present description.
Especially preferred as costabilizers are 2-hydroxyphenyl-benztriazoles and/or 2-hydroxyphenyl-triazines.
The examples below illustrate the invention further. All parts or percentages, in the examples as in the remainder of the description and in the claims, are by weight, unless stated otherwise. Room temperature denotes a temperature in the range 20-30xc2x0 C., unless stated otherwise. In the examples, the following abbreviations are used:
Examples 1 to 5 describe the preparation of educts useful for preparing compounds of the formula I.